CN107170955B - A kind of facilitate disassembles the lithium ion battery recycled, production method and dismantling recovery method - Google Patents
A kind of facilitate disassembles the lithium ion battery recycled, production method and dismantling recovery method Download PDFInfo
- Publication number
- CN107170955B CN107170955B CN201710382441.6A CN201710382441A CN107170955B CN 107170955 B CN107170955 B CN 107170955B CN 201710382441 A CN201710382441 A CN 201710382441A CN 107170955 B CN107170955 B CN 107170955B
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- ion battery
- electrolyte
- electrode material
- dismantling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 79
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000011084 recovery Methods 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 239000003792 electrolyte Substances 0.000 claims abstract description 58
- 239000007772 electrode material Substances 0.000 claims abstract description 57
- 239000002904 solvent Substances 0.000 claims abstract description 44
- 239000012530 fluid Substances 0.000 claims abstract description 33
- 238000004064 recycling Methods 0.000 claims abstract description 20
- 239000007767 bonding agent Substances 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 23
- 229910052744 lithium Inorganic materials 0.000 claims description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- 239000000956 alloy Substances 0.000 claims description 14
- 239000007773 negative electrode material Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000011800 void material Substances 0.000 claims description 9
- 210000005069 ears Anatomy 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 4
- 230000033116 oxidation-reduction process Effects 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- 238000005056 compaction Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims description 2
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- 239000002134 carbon nanofiber Substances 0.000 claims 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 239000008247 solid mixture Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 31
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 238000007872 degassing Methods 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- 239000011267 electrode slurry Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000012155 injection solvent Substances 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- -1 Acieral Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- ADKPKEZZYOUGBZ-UHFFFAOYSA-N [C].[O].[Si] Chemical compound [C].[O].[Si] ADKPKEZZYOUGBZ-UHFFFAOYSA-N 0.000 description 1
- OQPHEVHDBFEJRQ-UHFFFAOYSA-N [Li].P(O)(O)(O)=O Chemical compound [Li].P(O)(O)(O)=O OQPHEVHDBFEJRQ-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0409—Methods of deposition of the material by a doctor blade method, slip-casting or roller coating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
A kind of lithium ion battery for facilitating dismantling to recycle, there is the gas or fluid path communicated with the outside world on its shell, gas or the external valve of fluid path, in normal use, as gas passage, for the gas generated in lithium ion battery to be periodically discharged, when disassembling recycling, as fluid path, it is extracted out for being injected into lithium ion battery after solvent is sufficiently mixed with internal electrode material and electrolyte, its production method is also disclosed in the present invention, without bonding agent, the molding for being in close contact electrode and collector, the dismantling recovery method of the lithium ion battery is also disclosed simultaneously, pass through the fluid path on shell, inject solvent, liquid-solid mixture is formed with electrode material and electrolyte etc., the method extracted out from lithium ion battery.This method can make electrode material, electrolyte and collector and the diaphragm rate of recovery be greater than 98%, have many advantages, such as that cost recovery is low, safety and environmental protection.
Description
Technical field
The invention belongs to technical field of lithium ion, in particular to a kind of lithium ion battery that dismantling can be facilitated to recycle,
Production method and dismantling recovery method.
Background technique
Lithium ion battery has the advantages that storage energy density is big, in Vehicular dynamic battery and mobile electron class consumer goods side
Face is widely applied, and is the important component of new energy.Lithium ion battery passes through years development, forms the mature lithiumation that contains and closes
The positive electrode of object, and the negative electrode material of the charcoal with various types of graphite state.And the processing method for foring comparative maturity, i.e.,
Positive electrode and conductive agent, the blending such as bonding agent form slurry, and coating, roll-in, after solidification, are closely sticked to aluminium foil together
On.Negative electrode material and bonding agent are mixed to form slurry, coating, roll-in, after solidification, are closely sticked on copper foil together.It welds again
Upper tab, and be separated by with diaphragm, electrolyte is injected, finished battery is formed.
Due to the presence of bonding agent, so that lithium ion battery is after a failure, electrode material and collector (and the electricity of absorption
Solution liquid) it is difficult dismantling recycling, certain environmental pollution and the wasting of resources are caused, very big security risk is also created.
Summary of the invention
In order to overcome the disadvantages of the above prior art, the purpose of the present invention is to provide the lithiums that one kind can facilitate dismantling to recycle
Ion battery, production method and dismantling recovery method, do not use bonding agent, can facilitate dismantling, there is lithium ion battery
It imitates in the duty cycle and works normally, and can recycle various types of materials to the maximum extent, and not when needing to disassemble recycling
Cause environmental pollution.
To achieve the goals above, the technical solution adopted by the present invention is that:
A kind of lithium ion battery for facilitating dismantling to recycle, including shell 7 have on the shell 7 and to communicate with the outside world
Gas or fluid path 9, the gas or the external valve of fluid path 9, in normal use, as gas passage, for regular
The gas generated in discharge lithium ion battery, it is molten for being injected into lithium ion battery as fluid path when disassembling recycling
Agent is extracted out after being sufficiently mixed with internal electrode material and electrolyte 5.
The functional unit of the inside lithium ion cell includes electrode material, electrolyte 5, diaphragm 6, collector, tab,
In, in the electrode material, positive electrode 1a includes that can carry out the lithium-containing compound of body phase oxidation reduction charging and mixed with carbon materials
The lithium-containing compound of material, negative electrode material 1b include the charcoal of class graphite state, lithium titanate, kamash alloy, silicon-base alloy, germanium-base alloy,
Acieral, antimony-containing alloy and magnesium base alloy or silicon oxycarbide close object, and the electrode material granularity is 0.01-30 microns;
In the collector, the collector for anode is porous aluminum collector 3a, and the collector for cathode is porous
Copper current collector 3b, the collector void size are 10-30 times of electrode material maximum particle diameter;
The electrolyte 5 is nonaqueous electrolyte;
The diaphragm 6 is for separating positive composite pole piece 4a and cathode composite pole piece 4b, wherein positive composite pole piece 4a by
Positive electrode 1a and porous aluminum collector 3a are made, and cathode composite pole piece 4b is by negative electrode material 1b and porous copper current collector 3b system
At;
The tab includes aluminium pole ears 8a and copper polar ear 8b, is respectively welded at positive composite pole piece 4a and cathode composite pole piece
On 4b.
The lithium-containing compound for carrying out body phase oxidation reduction charging is LiFePO4, LiMn2O4, cobalt acid lithium, nickel cobalt manganese
One of sour lithium and nickel cobalt lithium aluminate are a variety of, it is described mixed with carbon material be carbon nanotube, graphene, active carbon and receive
One of rice carbon fiber is a variety of, and the nonaqueous electrolyte is the carbonic ester dissolved with lithium hexafluoro phosphate.
The electrode material is present in the gap of collector, and the two is in close contact by way of mechanical compaction,
It is bonded without using bonding agent.
The production method of the lithium ion battery of the present invention for facilitating dismantling to recycle, includes the following steps:
Step 1: anode sizing agent 2a is made in positive electrode 1a, with the mode of extruding, is filled to the collection for being used for anode
In the gap of fluid, and by way of roll-in, it is in close contact the two, positive composite pole piece 4a is formed, by the cathode
Slurry cathode 2b is made in material 1b;It with the mode of extruding, is filled in the gap for being used for the collector of cathode, and passes through roller
The mode of pressure is in close contact the two, forms cathode composite pole piece 4b;
Step 2: aluminium pole ears 8a and copper polar ear 8b is respectively welded in the anode composite pole piece 4a and cathode composite pole piece 4b,
Separated with diaphragm 6, multi-disc assembling;
Step 3: aluminum plastic film or metal-back punch forming being formed into shell 7, gas or fluid path 9 is above stayed, will assemble
Pole piece be packaged in shell 7, by dehydration, degassing and Aging Step, inject electrolyte 5 after, encapsulation, formed lithium ion battery
Product;
Step 4: when normal use, gas or the external valve of fluid path 9 periodically arrange the gas generated in lithium ion battery
Out, but not ambient atmos or moisture etc. is allowed to enter in lithium ion battery.
The dismantling recovery method of the lithium ion battery of the present invention for facilitating dismantling to recycle, includes the following steps:
Step 1: when lithium ion battery needs to disassemble recycling, by the external world through the gas or fluid path 9, to lithium from
Solvent is injected in sub- battery, solvent is enable to be sufficiently mixed with electrode material and electrolyte 5;
Step 2: switching extraneous pipeline, through the gas or fluid path 9, by inside lithium ion cell by electrode material
The liquid of material, electrolyte 5 and solvent composition consolidates mixture extraction;
Step 3: repeat the above steps 1-2, and all electrode materials of inside lithium ion cell are extracted out with electrolyte 5;
Step 4: the liquid of extraction being consolidated into mixture, by centrifuge separation, first recycles the small carbon material of bulk density;Then again
The lithium-containing compound or alloy material for recycling large bulk density, the liquid for removing electrode material is distilled, pure electricity is obtained
Liquid and pure solvent are solved, realizes and is recycled;
Step 5: electrode material and electrolyte will be removed, and dismantled with the clean casing of lithium ion battery of solvent washing, returned
Diaphragm 6, collector and sheathing material therein are received, is recycled.
In the step 1, the temperature for injecting solvent is 20-50 DEG C, and injection rate is 1-2 times of 5 mass of electrolyte, after injection
Oscillation 1-3 hours, enables solvent to be sufficiently mixed with electrode material and electrolyte 5.
The solvent is ether, vinyl carbonate, propylene carbonate, diethyl carbonate or NMP.
In the step 2, extracts the liquid out at 10-90KPa and consolidate mixture.
Compared with prior art, the beneficial effects of the present invention are:
1) porous metals collector is used, electrode material is filled in its gap, by roll-in, bonding agent can not had to
Under the premise of, guarantee the two effectively contact (internal resistance is low), the filling compaction rate of electrode material is high, the volume energy density of device
It is high.
2) when needing to disassemble recycling, by shell gases or fluid passage, excessive solvent is injected, former composite pole piece is molten
Swollen, then the method by vacuumizing, utilizes the small feature of electrode material granules granularity, it is convenient to by internal electrode material
Material, electrolyte are extracted out together.The rate of recovery of electrode material and electrolyte is set to improve 40-60%.
3) lithium ion battery after extraction electrode material and electrolyte is only left very clean collector, diaphragm and outer
Shell, but also the rate of recovery of this three samples material improves 20-35%.
Detailed description of the invention
Fig. 1 is the schematic diagram of manufacturing method for the lithium ion battery that the present invention can facilitate dismantling to recycle.
Fig. 2 is the dismantling recovery method schematic diagram for the lithium ion battery that the present invention can facilitate dismantling to recycle.
Specific embodiment
Below in conjunction with specific embodiment (including but not limited to following examples), present invention work is further retouched in detail
It states.
Embodiment 1
Referring to Fig.1, anode sizing agent 2a is conventionally made in positive electrode 1a (LiMn2O4,30 microns of partial size);With
The mode of extruding is filled to the gap of porous aluminum collector 3a (void size be positive electrode 1a maximum particle diameter 10 times)
In, and by way of roll-in, it is in close contact the two, forms positive composite pole piece 4a.By negative electrode material 1b (graphite, grain
10 microns of diameter), negative electrode slurry 2b is conventionally made;With the mode of extruding, it is (empty to be filled to porous copper current collector 3b
Gap size is 50 times of negative electrode material 1b maximum particle diameter) gap in, and by way of roll-in, be in close contact the two,
Form cathode composite pole piece 4b.Aluminium pole ears 8a and copper polar ear 8b is respectively welded in above-mentioned composite pole piece 4a and 4b, is divided with diaphragm 6
Every multi-disc assembling.
By aluminous shell stamping forming, gas or fluid path 9 are above stayed, shell 7 is made.Assembled pole piece is packaged in shell
In 7, by dehydration, degassing and Aging Step, after injection electrolyte 5 (methyl ethyl carbonate dissolved with lithium hexafluoro phosphate), encapsulation,
Form lithium ion battery product.When normal use, gas or the external valve of fluid path 9 will periodically generate in lithium ion battery
Gas discharge, but ambient atmos or moisture etc. is not allowed to enter in lithium ion battery.
When lithium ion battery needs to disassemble recycling, by the external world through gas or fluid path 9, injected into lithium ion battery
20 DEG C of solvent (ether), 2 times in 5 dosage of electrolyte of the controlling of injecting quantity.Lithium ion battery after injection solvent is shaken
It swings 2.5 hours, solvent is enable to be sufficiently mixed with electrode material and electrolyte 5.Switch extraneous pipeline, it is logical through gas or liquid
The liquid of inside lithium ion cell is consolidated mixture (electrode material, electrolyte and solvent) and extracted out at 10kPa by road 9.It repeats above-mentioned
Step totally 4 times, all electrode materials of inside lithium ion cell and electrolyte can be extracted out.The liquid of extraction is consolidated into mixture, it will
The liquid of extraction consolidates mixture, by centrifuge separation, first recycles the small carbon material of bulk density;Then recycling large bulk density
Lithium-containing compound or alloy material.The liquid (solvent and electrolyte) of electrode material will be removed, is distilled, obtain pure electrolysis
Liquid and pure solvent are realized and are recycled.Electrode material and electrolyte, and the lithium ion battery clean with solvent washing will be removed
Shell forcible entry.Recycle diaphragm 6 therein, collector and sheathing material (shell 7, aluminium pole ears 8a, copper polar ear 8b, gas or liquid
Access 9), it is recycled.
Embodiment 2
Referring to Fig.1, by positive electrode 1a (mixed with the phosphoric acid lithium of carbon nanotube, the mass fraction of carbon nanotube is 1%,
0.01 micron of partial size) anode sizing agent 2a is conventionally made;With the mode of extruding, it is filled to porous aluminum collector 3a
In the gap of (void size be positive electrode 1a maximum particle diameter 10 times), and by way of roll-in, connect the two closely
Touching forms positive composite pole piece 4a.By negative electrode material 1b (graphite, 30 microns of partial size), negative electrode slurry is conventionally made
2b;With the mode of extruding, it is filled to porous copper current collector 3b (void size be negative electrode material 1b maximum particle diameter 30 times)
Gap in, and by way of roll-in, be in close contact the two, form cathode composite pole piece 4b.By above-mentioned composite pole piece
Aluminium pole ears 8a and copper polar ear 8b is respectively welded in 4a and 4b, is separated with diaphragm 6, multi-disc assembling.
By stainless steel case punch forming, gas or fluid path 9 are above stayed, shell 7 is made.Assembled pole piece is packaged in
In shell 7, by dehydration, degassing and Aging Step, after injection electrolyte 5 (diethyl carbonate dissolved with lithium hexafluoro phosphate),
Encapsulation forms lithium ion battery product.When normal use, gas or the external valve of fluid path 9 will periodically produce in lithium ion battery
Raw gas discharge, but ambient atmos or moisture etc. is not allowed to enter in lithium ion battery.
Referring to Fig. 2, when lithium ion battery needs to disassemble recycling, by the external world through gas or fluid path 9, to lithium-ion electric
Inject 50 DEG C of solvent (NMP) in pond, 1.8 times in 5 dosage of electrolyte of the controlling of injecting quantity.By the lithium-ion electric after injection solvent
Pond carries out oscillation 2 hours, and solvent is enable to be sufficiently mixed with electrode material and electrolyte 5.Switch extraneous pipeline, through gas or
The liquid of inside lithium ion cell is consolidated mixture (electrode material, electrolyte and solvent) and extracted out at 90kPa by fluid path 9.Weight
Multiple above-mentioned steps totally 3 times, all electrode materials of inside lithium ion cell and electrolyte can be extracted out.The liquid of extraction is mixed admittedly
Body is filtered recycling electrode material granules.The liquid (solvent and electrolyte) of electrode material will be removed, is distilled, obtained
Pure electrolyte and pure solvent are realized and are recycled.Electrode material and electrolyte, and the lithium clean with solvent washing will be removed
The forcible entry of ion battery shell.Diaphragm 6, collector and sheathing material therein are recycled, is recycled.
Embodiment 3
Referring to Fig.1, by positive electrode 1a (mixed with the nickle cobalt lithium manganate of graphene and superP, graphene and superP's
Mass fraction is 0.1% and 3%, 0.1 micron of partial size) anode sizing agent 2a is conventionally made;With the mode of extruding, by it
It is filled in the gap of porous aluminum collector 3a (void size be positive electrode 1a maximum particle diameter 20 times), and passes through roll-in
Mode is in close contact the two, forms positive composite pole piece 4a.By negative electrode material 1b, (silicon oxygen carbon negative pole material, partial size 30 are micro-
Rice), negative electrode slurry 2b is conventionally made;With the mode of extruding, it is filled to porous copper current collector 3b (void size
30 times of negative electrode material 1b maximum particle diameter) gap in, and by way of roll-in, be in close contact the two, formed negative
Pole composite pole piece 4b.Aluminium pole ears 8a and copper polar ear 8b is respectively welded in above-mentioned composite pole piece 4a and 4b, is separated with diaphragm 6, multi-disc
Assembling.
By aluminum plastic film punch forming, gas or fluid path 9 are above stayed, shell 7 is made.Assembled pole piece is packaged in shell
In body 7, by dehydration, degassing and Aging Step, after injection electrolyte 5 (propylene carbonate dissolved with lithium hexafluoro phosphate), envelope
Dress forms lithium ion battery product.When normal use, gas or the external valve of fluid path 9 will periodically generate in lithium ion battery
Gas discharge, but do not allow ambient atmos or moisture etc. enter lithium ion battery in.
Referring to Fig. 2, when lithium ion battery needs to disassemble recycling, by the external world through gas or fluid path 9, to lithium-ion electric
Inject 60 DEG C of solvent (propylene carbonate) in pond, 1.3 times in 5 dosage of electrolyte of the controlling of injecting quantity.After injection solvent
Lithium ion battery carries out oscillation 1 hour, and solvent is enable to be sufficiently mixed with electrode material and electrolyte 5.Switch extraneous pipeline,
Through gas or fluid path 9, the liquid of inside lithium ion cell is consolidated into mixture (electrode material, electrolyte and solvent) in 10KPa
Lower extraction.It repeats the above steps totally 2 times, all electrode materials of inside lithium ion cell and electrolyte can be extracted out.It will extraction
Liquid consolidate mixture, be filtered recycling electrode material granules.The liquid (solvent and electrolyte) of electrode material will be removed, is carried out
Distillation obtains pure electrolyte and pure solvent, realizes and is recycled.Electrode material and electrolyte will be removed, and will be rushed with solvent
The casing of lithium ion battery of wash clean dismantles.Diaphragm 6, collector and sheathing material therein are recycled, is recycled.
Embodiment 4
Referring to Fig.1, by positive electrode 1a (mixed with the nickel cobalt lithium aluminate of graphene and carbon nanotube, graphene and carbon nanometer
The mass fraction of pipe is 0.1% and 0.3%, 0.05 micron of partial size) anode sizing agent 2a is conventionally made;With the side of extruding
Formula is filled in the gap of porous aluminum collector 3a (void size be positive electrode 1a maximum particle diameter 20 times), and is led to
The mode for crossing roll-in, is in close contact the two, forms positive composite pole piece 4a.By negative electrode material 1b, (tin alloy, partial size 3 are micro-
Rice), negative electrode slurry 2b is conventionally made;With the mode of extruding, it is filled to porous copper current collector 3b (void size
30 times of negative electrode material 1b maximum particle diameter) gap in, and by way of roll-in, be in close contact the two, formed negative
Pole composite pole piece 4b.Aluminium pole ears 8a and copper polar ear 8b is respectively welded in above-mentioned composite pole piece 4a and 4b, is separated with diaphragm 6, multi-disc
Assembling.
By aluminum plastic film punch forming, gas or fluid path 9 are above stayed, shell 7 is made.Assembled pole piece is packaged in shell
In body 7, by dehydration, degassing and Aging Step, after injection electrolyte 5 (vinyl carbonate dissolved with lithium hexafluoro phosphate), envelope
Dress forms lithium ion battery product.When normal use, gas or the external valve of fluid path 9 will periodically generate in lithium ion battery
Gas discharge, but do not allow ambient atmos or moisture etc. enter lithium ion battery in.
Referring to Fig. 2, when lithium ion battery needs to disassemble recycling, by the external world through gas or fluid path 9, to lithium-ion electric
Inject 30 DEG C of solvent (vinyl carbonate) in pond, 1 times in 5 dosage of electrolyte of the controlling of injecting quantity.By the lithium after injection solvent
Ion battery carries out oscillation 3 hours, and solvent is enable to be sufficiently mixed with electrode material and electrolyte 5.Switch extraneous pipeline, warp
The liquid of inside lithium ion cell is consolidated mixture (electrode material, electrolyte and solvent) at 50KPa by gas or fluid path 9
Extraction.It repeats the above steps totally 3 times, all electrode materials of inside lithium ion cell and electrolyte can be extracted out.By extraction
Liquid consolidates mixture, is filtered recycling electrode material granules.The liquid (solvent and electrolyte) of electrode material will be removed, is steamed
It evaporates, obtains pure electrolyte and pure solvent, realize and be recycled.Electrode material and electrolyte will be removed, and uses solvent washing
Clean casing of lithium ion battery forcible entry.Diaphragm 6, collector 3 and sheathing material therein are recycled, is recycled.
Claims (7)
1. the dismantling recovery method for the lithium ion battery that one kind can facilitate dismantling to recycle, the lithium ion battery includes shell (7),
There is the gas or fluid path (9) communicated with the outside world, the gas or fluid path (9) external valve on the shell (7),
When normal use, as gas passage, for the gas generated in lithium ion battery to be periodically discharged, when disassembling recycling, as
Fluid path is extracted out for being injected after solvent is sufficiently mixed with internal electrode material and electrolyte (5) into lithium ion battery,
It is characterized by: dismantling recycling includes the following steps:
Step 1: when lithium ion battery needs to disassemble recycling, by the external world through the gas or fluid path (9), to lithium ion
Solvent is injected in battery, and solvent is enable to be sufficiently mixed with electrode material and electrolyte (5);
Step 2: switch extraneous pipeline, through the gas or fluid path (9), by inside lithium ion cell by electrode material,
The liquid of electrolyte (5) and solvent composition consolidates mixture extraction;
Step 3: repeat the above steps 1-2, and all electrode materials of inside lithium ion cell and electrolyte (5) are extracted out;
Step 4: the liquid of extraction being consolidated into mixture, by centrifuge separation, first recycles the small carbon material of bulk density;Then recycling
The lithium-containing compound or alloy material of large bulk density, the liquid for removing electrode material is distilled, and obtains pure electrolyte
With pure solvent, realizes and be recycled;
Step 5: electrode material and electrolyte will be removed, and dismantled with the clean casing of lithium ion battery of solvent washing, it is recycled
In diaphragm (6), collector and sheathing material, be recycled.
2. the dismantling recovery method for the lithium ion battery that dismantling can be facilitated to recycle according to claim 1, which is characterized in that institute
It states in step 1, the temperature for injecting solvent is 20-50 DEG C, and injection rate is 1-2 times of electrolyte (5) quality, vibrates 1-3 after injection
Hour, so that solvent is sufficiently mixed with electrode material and electrolyte (5).
3. the dismantling recovery method of the lithium ion battery according to claim 1 or claim 2 for facilitating dismantling to recycle, feature exist
In the solvent is ether, vinyl carbonate, propylene carbonate, diethyl carbonate or NMP.
4. the dismantling recovery method for the lithium ion battery that dismantling can be facilitated to recycle according to claim 1, which is characterized in that institute
It states in step 2, extracts the liquid out at 10-90KPa and consolidate mixture.
5. the dismantling recovery method for the lithium ion battery that dismantling can be facilitated to recycle according to claim 1, which is characterized in that institute
The functional unit for stating inside lithium ion cell includes electrode material, electrolyte (5), diaphragm (6), collector, tab, wherein institute
It states in electrode material, positive electrode (1a) includes that can carry out the lithium-containing compound of body phase oxidation reduction charging and mixed with carbon material
Lithium-containing compound, negative electrode material (1b) include charcoal, lithium titanate, kamash alloy, silicon-base alloy, germanium-base alloy, the aluminium of class graphite state
Based alloy, antimony-containing alloy and magnesium base alloy or silicon oxycarbide close object, and the electrode material granularity is 0.01-30 microns;
In the collector, the collector for anode is porous aluminum collector (3a), and the collector for cathode is Porous Cu
Collector (3b), the collector void size are 10-30 times of electrode material maximum particle diameter;
The electrolyte (5) is nonaqueous electrolyte;
The diaphragm (6) is for separating positive composite pole piece (4a) and cathode composite pole piece (4b), wherein positive composite pole piece
(4a) is made of positive electrode (1a) and porous aluminum collector (3a), and cathode composite pole piece (4b) is by negative electrode material (1b) and porous
Copper current collector (3b) is made;
The tab includes aluminium pole ears (8a) and copper polar ear (8b), is respectively welded at positive composite pole piece (4a) and cathode composite pole
On piece (4b).
6. the dismantling recovery method for the lithium ion battery that dismantling can be facilitated to recycle according to claim 5, which is characterized in that institute
It is LiFePO4, LiMn2O4, cobalt acid lithium, nickle cobalt lithium manganate and nickel that the lithium-containing compound of body phase oxidation reduction charging can be carried out by, which stating,
One of cobalt lithium aluminate is a variety of, it is described mixed with carbon material be carbon nanotube, graphene, active carbon and carbon nano-fiber in
It is one or more, the nonaqueous electrolyte be dissolved with lithium hexafluoro phosphate carbonic ester.
7. the dismantling recovery method for the lithium ion battery that dismantling can be facilitated to recycle according to claim 5, which is characterized in that institute
It states electrode material to be present in the gap of collector, the two is in close contact by way of mechanical compaction, without using bonding
Agent bonding.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710382441.6A CN107170955B (en) | 2017-05-26 | 2017-05-26 | A kind of facilitate disassembles the lithium ion battery recycled, production method and dismantling recovery method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710382441.6A CN107170955B (en) | 2017-05-26 | 2017-05-26 | A kind of facilitate disassembles the lithium ion battery recycled, production method and dismantling recovery method |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107170955A CN107170955A (en) | 2017-09-15 |
CN107170955B true CN107170955B (en) | 2019-07-12 |
Family
ID=59821219
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710382441.6A Active CN107170955B (en) | 2017-05-26 | 2017-05-26 | A kind of facilitate disassembles the lithium ion battery recycled, production method and dismantling recovery method |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107170955B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110556504B (en) * | 2018-05-30 | 2022-05-27 | 北京好风光储能技术有限公司 | Full life cycle operation mode of lithium battery capable of injecting/extracting liquid |
CN114006072B (en) * | 2021-11-01 | 2023-12-26 | 武汉蔚能电池资产有限公司 | Easy-to-detach battery electrode plate and detachment method thereof |
DE102022114782A1 (en) | 2022-06-13 | 2022-08-18 | Daimler Truck AG | Electrical energy storage |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103430354A (en) * | 2011-02-22 | 2013-12-04 | 住友电气工业株式会社 | Battery electrode and battery |
CN103825064A (en) * | 2014-02-27 | 2014-05-28 | 北京工业大学 | Demonstration process for recovering waste and old dynamic lithium iron phosphate cell in environmental protection mode |
CN104335389A (en) * | 2012-05-17 | 2015-02-04 | 丰田自动车株式会社 | Method for manufacturing cell |
CN105098284A (en) * | 2015-09-17 | 2015-11-25 | 国网北京市电力公司 | Battery recycling and disposal method and device |
CN105324880A (en) * | 2013-06-24 | 2016-02-10 | 丰田自动车株式会社 | Non-aqueous electrolyte secondary cell and method for manufacturing same |
-
2017
- 2017-05-26 CN CN201710382441.6A patent/CN107170955B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103430354A (en) * | 2011-02-22 | 2013-12-04 | 住友电气工业株式会社 | Battery electrode and battery |
CN104335389A (en) * | 2012-05-17 | 2015-02-04 | 丰田自动车株式会社 | Method for manufacturing cell |
CN105324880A (en) * | 2013-06-24 | 2016-02-10 | 丰田自动车株式会社 | Non-aqueous electrolyte secondary cell and method for manufacturing same |
CN103825064A (en) * | 2014-02-27 | 2014-05-28 | 北京工业大学 | Demonstration process for recovering waste and old dynamic lithium iron phosphate cell in environmental protection mode |
CN105098284A (en) * | 2015-09-17 | 2015-11-25 | 国网北京市电力公司 | Battery recycling and disposal method and device |
Also Published As
Publication number | Publication date |
---|---|
CN107170955A (en) | 2017-09-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102044666B (en) | Method for preparing lithium iron phosphate composite material for lithium cells | |
CN103187551B (en) | Lithium ion liquid flow battery | |
CN107170955B (en) | A kind of facilitate disassembles the lithium ion battery recycled, production method and dismantling recovery method | |
CN106450467A (en) | Lithium supplementing method for energy storage device | |
CN101609884B (en) | Method for preparing negative pole material SnS2 of lithium ion battery | |
CN103515657B (en) | Battery | |
CN104282935B (en) | A kind of lithium titanate battery and manufacture method | |
CN110289408A (en) | Nano-silicon and silicon/carbon composite and preparation method and application based on cutting scrap silicon | |
CN103943377A (en) | Preparation method of porous electrode | |
CN103515609B (en) | THAQ/ graphene composite material, its preparation method, anode and lithium ion battery | |
CN106848475A (en) | A kind of waste and old lithium ion battery pre-treatment green reclaim processing method and its equipment | |
CN202134609U (en) | Sheet wrapping machine structure used for producing lead-acid storage battery plates | |
CN106099234B (en) | Method for electrolytically separating anode material and aluminum current collector in waste lithium ion battery | |
CN106356531A (en) | Cobalt and zinc binary metal coordination polymer, preparation method thereof, application of cobalt and zinc binary metal coordination polymer serving as lithium battery anode material | |
CN109103534B (en) | Recovery method of waste cobalt-containing lithium ion battery | |
CN109400905A (en) | A kind of metal organic framework Mn-BTC and preparation method and application | |
CN103008653A (en) | Carbon coated lead composite material and preparation method thereof | |
CN104638236B (en) | A kind of preparation method of the polyaniline of hollow core-shell structure/sulphur composite | |
CN106532141A (en) | Formation method of battery | |
Fu et al. | The surface coating strategy enhances the lithium storage performance of Ni3S2@ PPy self-supporting as anode materials for lithium-ion batteries | |
CN102005625A (en) | Process for treating wasted lithium cells | |
CN104979533A (en) | Graphene nano-belt wound germanium nanoparticle composite material preparation method | |
CN107482193A (en) | Silicon nanowire composite material jointly modified by nickel nanoparticles and silicon-nickel nano substances and preparation method thereof | |
CN102386440A (en) | High-power high-safety lithium ion secondary battery and preparation method thereof | |
CN111146007A (en) | Zinc ion hybrid supercapacitor and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |